Patent GB-1012792-A (GB)
Title: Stabilized poly-ª‡-olefines
IPC: C09K15/12
Filed: 1961-12-19
Abstract: A polyolefin composition contains as a stabilizer a polyester of the formula <FORM:1012792/C3/1> or <FORM:1012792/C3/2> wherein n is 1 to 20, R1 is H, alkyl, cycloalkyl or aryl, R is methylene, oxydimethylene, thiodimethylene, cycloalkylene or arylene, x is 0 to 10, and y is 2 or 3.  The polyolefin may be polyethylene, polypropylene, poly-(3-methylbutene - 1), poly - (4 - methylpentene - 1), poly - (pentene - 1), poly - (3,3 - dimethylbutene - 1), poly - (4,4 - dimethylbutene - 1), poly - (octene - 1), or poly - (decene - 1), and may be a solid resin or a wax.  The composition may also contain a phenolic antioxidant, e.g. as described in Specifications 932,252, 932,253, 943,771, 972,989 and 975,112, an alkylene- or alkylidene-bisphenol of specified formulae such as 2,21 - methylenebis - (4 - methyl - 6 - t-octylphenol) and 4,41 - n - butylidenebis - (2-methylphenol), a 4,41 - alkylenedioxybis-(alkylated phenol), or a hydroxyl-containing amine of specified formulae such as 4-hydroxy-41 - lauryldiphenylamine, 3 - t - butyl - 41-hydroxydiphenylamine, and N-acetyl-p-aminophenol. The weight ratio of polyester : phenolic antioxidant may be from 1 : 20 to 20 : 1. polypropylene may be stabilized with a mixpure of (a) a polyester from 4 : 41-thiodibutyric acid and ethylene glycol (M.W. 670) and 4,41-butylidenebis - (6 - t - butyl - m - cresol), 2,6-di-t-butyl-p-cresol, propyl gallate, 2,4,5-trihydroxybutyrophenone, 2 - t - butyl - 4 - (2,3-epoxypropyloxy) - phenol, 2,6 - bis - (21-hydroxy - 31 - t - butyl - 51 - methylbenzyl) - p - cresol, 4,41 - thiobis - (6 - t - butyl-m - cresol), 4,41 - thiobis - (6 - t - butyl - o - cresol), 2,21 - methylenebis - 6 - (1 - methylhexyl) - p - cresol, 2,21 - methylenebis - (6 - t-butyl - p - cresol or N - (4 - hydroxyphenyl)-morpholine; (b) 4,41-butylidenebis-(6-t-butyl-m-cresol and a polyester from 3,31-thiodipropionic acid and neopentyl glycol (M.W. 669 or 1,445) or from 3,31-thiodipropionic acid and ethylene glycol (M.W. 571); (c) 2-t-butyl-4-(2,3 - epoxypropyloxy) - phenol and the first or third polyester of (b); and (d) the polyester from 3,31-thiodipropionic acid (M.W. 669) and butylated hydroxyanisole. Additional combinations are disclosed for polypropylene, and similar combinations for polyethylene. It is shown that the polyester from thiodipivalic acid and neopentyl glycol (M.W. 811) does not have the stabilizing effect.  A polyester (M.W. 669) is prepared from 3,31 - thiodipropionic acid and neopentyl glycol by heating in dimethylpentanol containing titanium tetraisopropoxide, and finally refluxing the distilled product with water to convert the catalyst to TiO2.  Similar polyesters (M.W. 1,106 and 1,445) are prepared by varying the proportions of the reactants, and also from 4,41-thiodibutyric acid and ethylene glycol (M.W. 670 and 1,200), from thiodipivalic acid and neopentyl glycol (M.W. 811), 3,31-thiodipropionic acid and ethylene glycol (M.W. 571 and 1441), and 3,31-thiodipropionic acid and 1,5-pentanediol, 1,4-cyclohexanedimethanol, diethylene glycol, or b ,b 1-thiodiethanol. Other glycols are specified.  Esters of the thio acids may be used in the reaction, and a chainterminating agent such as a monobasic carboxylic acid, its ester or anhydride, or a monohydric alcohol or substituted alcohol may be employed.ALSO:Polyesters of the formula: <FORM:1012792/C2/1> wherein n is 1 to 20, R1 is H, alkyl, cycloalkyl or aryl, R is methylene, oxydimethylene, thiodimethylene, cycloalkylene or arylene, x is 0 to 10, and y is 2 or 3, are prepared by condensing 3,31-thiodipropionic acid or 4,41-thiodibutyric acid or an ester thereof with a glycol.  A chain-terminating agent, such as a monobasic carboxylic acid, its ester or anhydride, or a monohydric alcohol or substituted alcohol, may be employed.  A polyester (M.W. 669) is prepared from 3,31-thiodipropionic acid and neopentyl glycol by heating in dimethylpentanol containing titanium tetraisopropoxide, and finally refluxing the distilled product with water to convert the catalyst to TiO2.  Similar polyesters (M.W. 1,106 and 1,445) are prepared by varying the proportions of the reactants, and also from 4,41-thiodibutyric acid and ethylene glycol (M.W. 670 and 1,200), from thiodipivalic acid and neopentyl glycol (M.W. 811), 3,31-thiodipropionic acid and ethylene glycol (M.W. 571 and 1441), and 3,31-thiodipropionic acid and 1,5-pentanediol, 1,4-cyclohexanedimethanol, diethylene glycol, or b ,b 1-thiodiethanol.  Other glycols are specified.